The phosphinoboration of carbodiimides, isocyanates, isothiocyanates and CO2

Article abstract of DOI:10.1039/c7dt02305g

The transition metal-free addition of phosphinoboronate ester Ph₂PBpin (pin = 1,2-O₂C₂Me₄) to heterocumulenes including carbodiimides, isocyanates, isothiocyanates and carbon dioxide has been investigated. The corresponding 1,2-addition products were readily prepared at room temperature without the need of a catalyst or added base. Addition of methanol to the compounds derived from addition of Ph₂PBpin to carbodiimides, isocyanates, and isothiocyanates resulted in traditional hydrophosphination products. The methodology developed in this study provides a simple and elegant route for the generation of a wide range of functionalized phosphines. The phosphinoboronate ester Ph₂PBpin also selectively and reversibly adds to CO₂ at room temperature in a 1,2-manner.

Full text of DOI:10.1039/c7dt02305g

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LaFortune, D. Zhu, S. C. Kosnik, C. L. B. Macdonald, D. W. Stephan and S. Westcott, Dalton Trans., 2017,
DOI: 10.1039/C7DT02305G.
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PAPER
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Efficient extraction of sulfate from water using
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DOI: 10.1039/C7DT02305G
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PAPER
The Phosphinoboration of Carbodiimides, Isocyanates,
Isothiocyanates and CO2
Stephen J. Geier,a James H. W. LaFortune,b Diya Zhu,a,b Stephanie C. Kosnik,c Charles L. B.
Received 00th June 26 20xx,
Accepted 00th January 20xx
Macdonald,c Douglas W. Stephan,b* and Stephen A. Westcottc*
DOI: 10.1039/x0xx00000x
The transition metal-free addition of phosphinoboronate ester Ph 2PBpin (pin = 1,2-O2C2Me4) to
heterocumulenes including carbodiimides, isocyanates, isothiocyanates and carbon dioxide has been
www.rsc.org/
investigated
. The corresponding 1,2-addition products were readily prepared at room temperature
without the need of a catalyst or added base. Addition of methanol to the compounds derived from
addition of Ph2PBpin to carbodiimides, isocyanates, and isothiocyanates resulted in traditional
hydrophosphination products. The methodology developed in this study provides a simple and
elegant route for the generation of a wide range of functionalized phosphines.
The
phosphinoboronate ester Ph2PBpin also selectively and reversibly adds to CO2 at room temperature in
a 1,2-manner.
aminoboration reaction of alkynes that selectively generates 3-
borylated indoles.9d While there has been significant literature
describing the generation of phosphinoboron compounds, 11 the
corresponding addition of these species to unsaturated organic
substrates remains almost unexplored. Lerner and co-workers
recently demonstrated that a phosphinoborane derived from 9-
borafulvalene reacts with benzophenone to give the
corresponding 1,2-addition product exclusively.10a
Introduction
There has been recent considerable interest in the chemistry of
compounds containing boron-element bonds (B-E, where E =
H,1 B,2 Sn,3 Si,4 S,5 Se,6 O,7 etc). For instance, the hydroboration
of alkenes and alkynes (E = H) is a remarkably powerful and
useful reaction in organic synthesis, leading to the
functionalization of the site of unsaturation. 1 Although
analogous diboration (E = B)2 and borylation chemistry
(replacing a sp2 C-H bond with a BR2 group)8 are finding
increased use in organic synthesis, these reactions typically
functionalize the two sites equivalently or sacrifice one of the
boryl (BR2) groups. Reactions of unsaturated organics with
heavier main group elements (E = Se, Sn, Si, etc) usually require
Fig. 1. The addition of B-E bonds to organic substrates can be challenging as
a
catalyst and/or strong base and result in novel
chemo- and regioselectivity issues can complicate product distributions.
organodimetalloid compounds.3-6 Of these latter reactions the
silaboration of C-C multiple bonds is particularly promising. 4
The resulting silyl and boryl groups can be independently
transformed into different functional groups, however issues of
chemo- and regioselectivity can complicate such addition
reactions (Fig. 1).
Given the interest in the reactivity of main group-boron
compounds it is surprising that almost nothing is known about
addition chemistry of compounds containing single B-E bonds
where E = N9 or P10. For instance, an elegant and seminal study
published by Chong and Blum disclosed a gold-catalysed
Gentle and efficient ways to reduce aldimines and ketimines are
of considerable interest in the synthesis of a wide variety of
amines.12 Although hydrosilanes are well-known to reduce C=N
bonds, usually in the presence of a catalyst,13 considerably less
is known about the corresponding hydroboration, 14
diboration15 and silaboration (or silylboration)16 of imines.
Carbodiimides (RN=C=NR’) are an interesting subclass of imines
containing a central sp-hybridised carbon atom that have
attracted recent attention as synthons in a number of
transformations.17
For instance, the catalysed hydro-
phosphination of carbodiimides is a synthetic methodology for
the preparation of phosphaguanidine ligands, where P-H
additions generally proceed to give products containing a new
P-C bond.18 Known routes to phosphaguanidines typically
involve harsh reaction conditions or the use of a catalyst to
facilitate the hydrophosphination of carbodiimides.
a.Department of Chemistry and Biochemistry, Mount Allison University, Sackville,
NB E4L 1G8, Canada.
b.Department of Chemistry, University of Toronto, Toronto, ON M5S 3H6, Canada.
c. Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON
N9B 3P4, Canada.
Electronic Supplementary Information (ESI) available: Complete spectroscopic data
is available at DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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Unfortunately, the latter metal-catalysed routes are often Complete conversion of the starting materials was achieved and
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DOI: 10.1039/C7DT02305G
complicated by coordination of the starting phosphine, or the the product could be isolated in 82% yield. A singlet in the
resultant phosphaguanide product, to the metal centre and 11B{1H} NMR spectrum at 21.8 ppm is indicative of three-
ultimately poisons the active catalyst. An excellent review by coordinate boron bound to a nitrogen atom. 19l A singlet is also
Bange and Waterman eloquently outlines the current observed in the 31P{1H} NMR spectrum at 2.2 ppm. Interestingly,
challenges associated with catalysed hydrophosphination the central imine carbon atom is found at 164.2 ppm in the
reactions.18r
13C{1H} NMR spectrum but no coupling to the P atom is
As part of our programme designed at expanding B-E addition observed. Coupling constants in these species are known to vary
reactions, we have recently prepared phosphinoboronate with bond angles and the nature of the substituents. 18 For
esters containing single B-P bonds that add selectively to instance, the central carbon atom is observed at 154.8 ppm in
aldehydes, ketones and imines without the aid of a catalyst or the parent phosphaguadine Ph2PC(NHp-tol)(Np-tol) with a
1
base.10b,c These reactions proceed smoothly at room coupling constant of JPC = 38.7 Hz.18d However, to confirm the
temperature leading to addition of the electron-deficient boryl phosphinoboration product contained a newly-formed P-C
group to the electron-rich heteroatom with concurrent bond, a single crystal X-ray diffraction study was carried out on
formation of a new P-C bond (Scheme 1). Herein, we expand 1a (Fig. 2). The structural data confirms the sterically-less
the scope of B-P additions to reactions with heterocumulenes. hindered Zsyn conformation. Of interest are the angles around
Specifically Ph2PBpin (pin = 1,2-O2C2Me4) is shown to add to the the saturated amine nitrogen (N1) which are roughly trigonal
species E=C=E’ (E, E’ = O, NR; carbodiimides, isocyanates, and add up to 359.4o. This observation suggests there is
isothiocyanates and carbon dioxide), providing an considerable overlap with the nitrogen lone pair and the empty
unprecedented route to novel unsaturated products derived orbital on boron. Similar bond angles and distances have been
from 1,2 P/B additions.
reported for the analogous hydroboration products. 19l All
attempts to add a second equivalent of Ph2PBpin to 1a proved
unsuccessful.
E
Bpin
R2
E
1) n-BuLi
R1
O
O
R2
Ph2PH
P
B
Ph
Ph
R1
2) pinBOiPr
E = O, NR3
PPh2
Ph2PBpin
no added catalyst or base required
O
O
BCl
Ph2P(SiMe3)
Scheme 1 The Phosphinoboration of Aldehydes, Ketones, Aldimines and Ketimines.
Results and discussion
Carbodiimides
The addition of boron reagents to carbodiimides has received
Fig. 2. The molecular structures of 1a and 2a drawn at the 50% probability level and
considerable recent attention.19 Of singular interest is an hydrogen atoms omitted for clarity. Selected bond distances (Å) and angles (o): [1a] C(1)-
N(2) 1.271(2) C(1)-N(1) 1.424(2), C(1)-P(1) 1.8592(18), N(1)-B(1) 1.430(2); C(1)-N(1)-B(1)
119.92(15), C(1)-N(1)-C(20) 116.10(14), B(1)-N(1)-C(20) 123.38(14). [2a] C(1)-N(2)
1.261(2), C(1)-N(1) 1.4306(19), C(1)-P(1) 1.8649(16), N(1)-B(1) 1.416(2); B(1)-N(1)-C(1)
119.97(13), B(1)-N(1)-C(20) 123.11(13), C(1)-N(1)-C(20) 116.92(12).
elegant study by Hill and co-workers who demonstrated that β-
diketiminato magnesium alkyl complexes could be used to
catalyse the addition of HBpin to carbodiimides to give N-boryl
formamidine products in high yields.19k
Reactions of Ph2PBpin with the aliphatic carbodiimides N,N’-di-
R
C
R
C
i-propylcarbodiimide and N,N’-di-cyclohexylcarbodiimide gave
products 2a and 3a, respectively, as a 90:10 mixture of isomers
in solution. Isomeric mixtures of Zsyn and Esyn conformers are
typically observed in related phosphaguanidines. 19b,k A single
crystal X-ray diffraction study was also carried out on 2a (Fig. 2).
Crystallographic data is provided in Table 1. The angles around
the saturated amine nitrogen once again suggest a trigonal
environment with a sum being 360.0o. Not unexpectedly,
addition of Ph2PBpin to the unsymmetrical EtN=C=N(CH2)3NMe2
gave a mixture of products and isolation proved unsuccessful.
More remarkable is the observation that addition of a few drops
of methanol to 1a-3a resulted in the clean conversion to the
corresponding parent phosphaguanides 1b-3b.19k The
methodology developed herein therefore provides a gentle
N
Bpin
NH
R'N
C
NR
O
O
MeOH
P
B
Ph
Ph
R'N
R'N
-MeOBpin
no added catalyst
or base required
PPh2
PPh2
1a:
2a:
3a:
R = R' = p-C6H4CH3 (72%)
R = R' = CH(CH3)2 (74%)
R = R' = C6H11 (74%)
1-3b
Ph2PBpin
Scheme 2 The Phopshinoboration of Carbodiimides (Isolated Yields in Brackets).
Reactions of Ph2PBpin with three commercially-available
carbodiimides at room temperature (Scheme 2) were probed.
For example, addition of Ph2PBpin to N,N’-di-p-
tolylcarbodiimide
gave
the
corresponding
N-boryl
phosphaguanidine derivative 1a as the only new product in
solution (as ascertained by multinuclear NMR spectroscopy).
2 | Dalton Trans., 2017, 46, 1-9
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B(1) 1.4830(14), N(1)-C(20) 1.5030(15); C(1)-N(1)-B(1) 120.55(9), C(1)-N(1)-C(20)
route to a wide-array of phosphaguanines without the need of
employing a catalyst. Unfortunately, addition of methanol to
the mixture obtained from Ph2PBpin and the unsymmetrical
carbodiimide EtN=C=N(CH2)3NMe2 gave several products.
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120.30(9), B(1)-N(1)-C(20) 119.15(9).
DOI: 10.1039/C7DT02305G
Similar selectivities were also observed with isothiocyanates as
reactions proceeded smoothly at room temperature to
generate the corresponding 1,2-addition products 9a-12a
(Scheme 3). The molecular structure of the tert-butyl derivative
12a (Fig. 3), confirms addition occurred at the C=N double bond.
Addition of dry methanol to boron-containing derivatives 9a-
12a afforded phosphinothioamides 9b-12b along with
concomitant formation of MeOBpin. Although the use of both
4b-8b21 and 9b-12b22 have been investigated as ligands in
coordination chemistry, their use has been limited so far by the
inherent difficulties in preparing these species. As such, the
present methodology offers potential access to a wide array of
such ligands.
[please insert Table 1]
Isocyanates and Isothiocyanates
The reduction of isocyanates is of interest for the synthesis of
functionalised formamides.20 Grimme, Warren and co-
workers20d reported the hydroboration of bulky aryl isocyanates
with Pier’s borane (HB(C6F5)2). Using frustrated Lewis pairs, they
prepared formamide derivatives where the B-H bond added
selectively to the C=N double bond. Herein, reaction of
Ph2PBpin with either alkyl and aryl isocyanates gave selectively
the corresponding 1,2-addition products 4a-8a (Scheme 3).
Spectroscopic data are consistent with products arising from
addition to the C=N double bond as 13C{1H} NMR data shows a
peak around 180 ppm with coupling to the phosphorus atom
(JCP = 13-35 Hz). Likewise, the 11B{1H} NMR spectra show single
broad peaks at 24-25 ppm suggesting that the Bpin groups are
bound to the nitrogen atom and not the oxygen.
R
C
R
C
R
C
R
C
Ph2PBpin
+
MeOH
N
Bpin
N
Bpin
MeOH
NH
NH
S
-MeOBpin
O
O
-MeOBpin
S
RN
C
E
PPh2
PPh2
PPh2
PPh2
9-12b (84-90%)
4a: R = Ph (80%)
9a:
4-8b (78-94%)
R = Ph (78%)
10a: R = Bz (72%)
11a: R = Cy (72%)
12:a R = t-Bu (72%)
5a: R = p-C6H4NO2 (85%)
6a:
R = Et (76%)
: R = Cy (78%)
: R = t-Bu (76%)
7a
8a
Fig. 4. The molecular structures of 7b and one of the four unique molecules of 12a in the
asymmetric unit are drawn at the 50% probability level and hydrogen atoms omitted for
clarity. Selected bond distances (Å) and angles (o): [7b] C(1)-O(1) 1.221(5), C(1)-N(1)
1.332(5), C(1)-P(1) 1.892(4), N(1)-C(14) 1.463(5); O(1)-C(1)-N(1) 123.0(4), O(1)-C(1)-P(1)
123.0(3), N(1)-C(1)-P(1) 114.0(3), C(1)-N(1)-C(14) 122.2(4). [12a] C(11)-N(1) 1.342(2),
C(11)-S(1) 1.6567(19), C(11)-P(1) 1.8779(19), N(1)-B(1) 1.493(3), N(1)-C(120) 1.513(2);
C(11)-N(1)-B(1) 119.06(16), C(11)-N(1)-C(120) 124.08(17), B(1)-N(1)-C(120) 116.48(16).
Scheme 3 The Phopshinoboration of Isocyanates and Isothiocyanates (Isolated Yields in
Brackets).
To confirm the selectivity of these additions X-ray diffraction
studies on 6a and 8a were carried out (Fig. 3). The boryl (Bpin)
group is bound to the nitrogen as a new P—C bond is formed
where bond distances and angles are similar to previously
Carbon Dioxide
reported
structures.20
The
corresponding
phosphinoformamide derivatives 4b-8b are readily prepared in
high yields by the simple addition of methanol. Confirmation of
these products was obtained from a solid-state X-ray diffraction
study of the cyclohexyl derivative 7b (shown in Fig. 4).
The corresponding reaction of Ph2PBpin with CO2 also proceeds
at room temperature to give the 1,2-addition product 13 where
the PPh2 group has added to the carbon atom and the
electrophilic Bpin group has added to one of the oxygen atoms
(Scheme 4). A significant amount of research has recently
focussed on the reduction of CO2 using boron reagents.23 The
13C{1H} NMR spectrum shows a doublet at 177.5 ppm with
coupling to the 31P atom (JCP = 16 Hz). Likewise, a broad singlet
at 22 ppm is observed in the 11B{1H} NMR data corresponding
a three coordinate Bpin group bound to an oxygen atom. Efforts
to obtain single crystals of 13 were unsuccessful, nonetheless,
all spectroscopic data are consistent with the formulation of 13.
Similar reduction products arising from the addition of CO 2 to a
combination of a phosphinimines and B(C6F5)3 have been
previously reported.24 Interestingly, addition of dry methanol to
13 gave MeOBpin, PPh2H along with reformation of CO2.
Analogous reactivity was observed upon addition of 13 to
benzaldehyde. As such, Ph2PBpin provides a unique source for
the reversible and selective trapping of CO2 and current efforts
Fig. 3. The molecular structures of 6a and 8a drawn at the 50% probability level and
hydrogen atoms omitted for clarity. Selected bond distances (Å) and angles (o): [6a] C(1)-
O(1) 1.2156(14), C(1)-N(1) 1.3820(13), C(1)-P(1) 1.8927(12), N(1)-B(1) 1.4424(14), N(1)-
C(20) 1.4822(13); C(1)-N(1)-B(1) 126.03(9), C(1)-N(1)-C(20) 116.25(9), B(1)-N(1)-C(20)
117.71(9). [8a] C(1)-O(1) 1.2235(13), C(1)-N(1) 1.3570(14), C(1)-P(1) 1.8894(11), N(1)-
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are focussed on designing alternate phosphinoboranes for this standard Schlenk techniques or in an MBraun LabMaster
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capture process.25 Attempts to add a second equivalent of glovebox. Elemental Analysis was perforDmOeI:d10a.t10t3h9e/CU7DnTiv0e2r3s0i5tyG
Ph2PBpin to CO2 proved unsuccessful.
of Windsor using a Perkin Elmer 2400 combustion CHN analyser.
Preparation of compounds 1a-12a
General procedure: Phosphinoboration of Carbodiimides,
Isocyanates and Isothiocyanates. A mixture of Ph2PBpin (100
mg, 0.320 mmol) and substrate (0.32 mmol for 1a-7a and 9a-
11a; 0.64 mmol for 8a and 12a) in toluene (5 mL) was stirred for
the prescribed time at room temperature. The solvent was
removed under vacuum and the residue was either washed with
hexane (method A) - or recrystallized from hexane (method B).
Scheme 4 The Phopshinoboration of Carbon Dioxide (Isolated Yield in Brackets).
Conclusions
In summary, we have shown that the novel phosphinoboronate
ester Ph2PBpin selectively adds to heterocumulenes including Synthesis
of
1,1-diphenyl-N-(4,4,5,5-tetramethyl-1,3,2-
both alkyl and aryl carbodiimides, isocyanates, isothiocyanates dioxaborolan-2-yl)-N,N'-di-p-tolylphosphinecarboximidamide
and carbon dioxide to give the corresponding 1,2-addition (1a): This mixture was allowed to stir for 18 h and the product
products. Addition of methanol to the compounds derived from was isolated using method A. Colourless crystalline solid. Yield:
addition of carbodiimides, isocyanates, and isothiocyanates 82% (140 mg); mp: 117-120°C; Anal. Calcd. For C33H36BN2O2P:
afforded the corresponding hydrophosphination products. (534.44): C, 74.16; H, 6.79; N, 5.24. Found: C, 74.33; H, 6.96; N,
These latter species are typically prepared by a catalysed 5.09. 1H NMR (CDCl3): δ: 7.59 (t, J = 7.8 Hz, 4H, Ar), 7.29-7.23 (ov
addition of primary or secondary phosphines to these m, 6H, Ar), 7.01-6.97 (ov m, 6H, Ar), 6.78 (d, J = 7.0 Hz, 2H, Ar),
substrates and are further complicated by interactions with the 2.30 (s, 3H, Me), 2.23 (s, 3H, Me), 0.88 (s, 12H, pin). 11B{1H} NMR
catalyst. The present methodology developed avoids use of a (CDCl3): δ 21.8 (s). 13C{1H} NMR (CDCl3): δ 164.2, 146.6 (d, JCP
=
catalyst and provides a simple route to the generation of a 5.7 Hz), 139.2, 135.5 (d, JCP = 5.6 Hz), 135.3 (d, JCP = 21.1 Hz),
range of functionalized phosphines. In the case of the reaction 133.7, 133.6, 129.3 (d, JCP = 14.4 Hz), 128.9, 128.0 (d, JCP = 7.7
with CO2, this reaction is shown to be reversible. On-going Hz), 124.3, 120.8, 83.3, 24.2, 21.0. 31P{1H} NMR (CDCl3): δ 2.2 (s).
efforts are exploring the utility of these products as ambiphilic
ligands, and the potential of related phosphinoboronate esters Synthesis
of
N,N'-diisopropyl-1,1-diphenyl-N-(4,4,5,5-
in carbon dioxide capture. The results of these studies will be tetramethyl-1,3,2-dioxaborolan-2-
reported in due course.
yl)phosphinecarboximidamide (2a): This mixture was allowed to
stir for 18 h and the product was isolated using method B.
Colourless crystalline solid. Yield: 74% (123 mg); mp: 83.5-
84.5°C; Anal. Calcd. For C25H36BN2O2P: (438.36): C, 68.50; H,
Experimental
General conditions and methods
1
8.28; N, 6.39. Found: C, 68.12; H, 8.00; N, 6.47. H NMR (CDCl3):
δ 7.58 (br, 4H, Ar), 7.27-7.18 (m, 6H, Ar), 3.92 (sept, J = 6.2 Hz,
major, 1H, NCH), 3.65 (d q, J = 2.6 Hz, minor, NCH), 3.38 (d q, J
= 2.6 Hz, major, 1H, NCH), 1.10 (s, 12H, pin), 1.09-0.97 (ov m,
12H, CH(CH3)2). 11B{1H} NMR (CDCl3): δ 21.6. 13C{1H} NMR
(CDCl3): δ 161.2 (d, JCP = 7.7 Hz), 136.6, 135.0 (d, JCP = 17.2 Hz),
All reagents and solvents, unless otherwise noted, were
purchased from commercial sources and used without further
purification. Solvents were distilled over appropriate drying
agents under dinitrogen: CH2Cl2 over CaH2; hexane, benzene
and toluene over freshly wired sodium. CDCl3 was purchased
from Cambridge Isotope Laboratories, degassed by three
freeze-pump-thaw cycles and stored in a dark place over oven-
activated 4Å molecular sieves. Ph2PBpin was prepared as
previously reported.10b Compounds 1b,18d 2b,26a 3b,26a 4b,26b
7b,18n,26b and 9b18p,q,26b,c have been reported previously.
134.4 (d, JCP = 19.2 Hz), 128.5, 128.1 (d, JCP = Hz), 127.9 (d, JCP
=
7.7 Hz), 82.2, 51.3 (d, JCP = 14.4 Hz, minor), 50.7 (d, JCP = 4.8 Hz),
49.0 (d, JCP = 8.6 Hz), 24.7, 24.5, 23.7, 22.8, 22.7. 31P{1H} NMR
(CDCl3): δ 0.6 (minor), -0.7 (major).
Synthesis
of
N,N'-dicyclohexyl-1,1-diphenyl-N-(4,4,5,5-
tetramethyl-1,3,2-dioxaborolan-2-
NMR spectra were recorded on Bruker AvanceIII-400 MHz ( 1H:
400 MHz; 11B: 128 MHz and 13C: 100 MHz) and Agilent DD2-500
MHz (13C: 126 MHz and 31P: 202 MHz), or JEOL JNM-GSX400 (1H:
400 MHz; 11B: 128 MHz; 13C: 100 MHz and 31P: 162 MHz)
spectrometers. Chemical shifts (δ) are reported in ppm [relative
yl)phosphinecarboximidamide (3a): This mixture was allowed to
stir for 18 h and the product was isolated using method B.
White solid. Yield: 123 mg (74%); mp: 90.5-93.5°C; Anal. Calcd.
For C31H44BN2O2P: (518.49): C, 71.81; H, 8.55; N, 5.40. Found:
1
C, 71.58; H, 8.76; N, 5.30. H NMR (CDCl3): δ 7.63-7.55 (ov, m,
.
to residual solvent peaks (1H and 13C), external BF3 OEt2 (11B) or
4H, Ar), 7.27 (m, 6H, Ar), 3.62 (br, 1H, NCH), 2.85 (br, 1H, NCH),
1.67-1.17 (ov, m, 20H, Cy), 1.11 (s, 12H, pin). 11B{1H} NMR
(CDCl3): δ 22.4 (s). 13C{1H} NMR (CDCl3): δ 161.1 (d, JCP = 7.7 Hz),
136.8, 135.0, 134.4 (d, JCP = 20.1 Hz), 128.5, 128.1 (d, JCP = 7.7
Hz), 127.8 (d, JCP = 6.7 Hz), 82.1, 59.6 (d, JCP = 12.5 Hz, minor),
59.1 (d, JCP = 5.8 Hz), 57.4 (d, JCP = 6.7 Hz), 33.3, 32.9, 32.7, 26.7,
H3PO4 (31P)]. Multiplicities are reported as singlet (s), doublet
(d), triplet (t), quartet (q), quintet (quint), multiplet (m),
overlapping (ov), and broad (br). Melting points were measured
uncorrected with a Stuart SMP30 apparatus. All manipulations
were performed under an atmosphere of dinitrogen using
4 | Dalton Trans., 2017, 46, 1-9
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26.0, 25.8, 25.6, 25.5, 24.7, 24.5. 31P{1H} NMR (CDCl3): δ 0.0 isolated using method A. White solid. Yield: 100 mg (76%); mp:
View Article Online
DOI: 10.1039/C7DT02305G
(minor), -0.7 (major).
119.1-120.5°C; Anal. Calcd. For C23H BNO3P: (411.29): C,
31
H, 7.60; N, 3.41. Found: C, 67.01; H, 7.21; N, 3.43. 1H NMR
Synthesis of N-1,1-triphenyl-N-(4,4,5,5-tetramethyl-1,3,2- (CDCl3): δ 7.49 (m, 4H, Ar), 7.35-7.31 (ov m, 6H, Ar), 7.19 (d, J =
dioxaborolan-2-yl)phosphinecarboxamide (4a): This mixture 8.7 Hz, 2H, Ar), 1.43 (s, 9H, tBu), 1.38 (s, 12H, pin). 11B{1H} NMR
was allowed to stir for 6 h and the product was isolated using (CDCl3): δ 25.2 (s). 13C{1H} NMR (CDCl3): δ 176.4 (d, JCP = 12.5
method A. White solid. Yield: 110 mg (80%); mp: 123-125°C; 134.6 (d, JCP = 8.6 Hz), 134.0 (d, JCP = 19.2 Hz), 129.1, 128.4 (d,
Anal. Calcd. For C25H27BNO3P: (431.28): C, 69.62; H, 6.31; N, JCP = 6.7 Hz), 84.9, 56.8 (d, JCP = 7.7 Hz), 28.9, 25.4, 25.4. 31P{1H}
1
3.25. Found: C, 69.80; H, 6.45; N, 3.29. H NMR (CDCl3): δ 7.40 NMR (CDCl3): δ 3.5 (s).
(m, 4H, Ar), 7.33-7.30 (ov m, 6H, Ar), 7.25-7.20 (ov m, 3H, Ar),
7.01 (d, J = 6.9 Hz, 2H, Ar), 1.06 (s, 12H, pin). 11B{1H} NMR Synthesis of N-1,1-triphenyl-N-(4,4,5,5-tetramethyl-1,3,2-
(CDCl3): δ 25.2 (s). 13C{1H} NMR (CDCl3): δ 184.6, 139.5 (d, JCP
=
dioxaborolan-2-yl)phosphinecarbothioamide (9a): This mixture
2.9 Hz), 134.8 (d, JCP = 20.1 Hz), 134.7, 129.2, 128.9, 128.6, 128.4 was allowed to stir for 6 and the product was isolated using
(d, JCP = 5.7 Hz), 127.1, 84.4, 24.2. 31P{1H} NMR (CDCl3): δ 9.5 (s). method A. Yellow solid. Yield: 112 mg (78%); mp: 147-149°C;
Anal. Calcd. For C25H27BNO2PS: (447.34): C, 67.12; H, 6.08; N,
1
Synthesis
of
N-(4-nitrophenyl)-1,1-diphenyl-N-(4,4,5,5- 3.13. Found: C, 66.88; H, 5.74; N, 3.07. H NMR (CDCl3): δ 7.42
tetramethyl-1,3,2-dioxaborolan-2-yl)phosphinecarboxamide
(m, 4H, Ar), 7.34-7.23 (ov m, 9H, Ar), 7.25-7.20 (ov m, 3H, Ar),
(5a): This mixture was allowed to stir for 6 h and the product 7.04 (d, J = 7.4 Hz, 2H, Ar), 1.09 (s, 12H, pin). 11B{1H} NMR
was isolated using method A. Yellow solid. Yield: 130 mg (85%); (CDCl3): δ 24.1 (s). 13C{1H} NMR (CDCl3): δ: 225.0 (d, JCP = 44 Hz),
mp: 94-95°C; Anal. Calcd. For C25H26BN2O5P: (476.28): C, 63.05; 143.5 (d, JCP = 3.8 Hz), 136.5 (d, JCP = 6.7 Hz), 134.9 (d, JCP = 21.1
H, 5.50; N, 5.88. Found: C, 62.67; H, 5.74; N, 5.87. 1H NMR Hz), 129.4, 129.1, 129.0, 128.4 (d, JCP = 7.7 Hz), 127.9, 127.4,
(CDCl3): δ 8.14 (d, J = 8.8 Hz, 2H, Ar), 7.41 (m, 4H, Ar), 7.38-7.33 85.1, 24.2. 31P{1H} NMR (CDCl3): δ 26.7 (s).
(ov m, 6H, Ar), 7.19 (d, J = 8.7 Hz, 2H, Ar), 1.05 (s, 12H, pin).
11B{1H} NMR (CDCl3): δ: 23.9 (s). 13C{1H} NMR (CDCl3): δ 184.6 (d, Synthesis of N-benzyl-1,1-diphenyl-N-(4,4,5,5-tetramethyl-
JCP = 34.5 Hz), 146.5, 145.8 (d, JCP = 1.9 Hz), 134.7 (d, JCP = 20.1 1,3,2-dioxaborolan-2-yl)phosphinecarbothioamide (10a): This
Hz), 134.1 (d, JCP = 7.7 Hz), 129.7 (d, JCP = 21.1 Hz), 128.6 (d, JCP mixture was allowed to stir for 18 h and the product was
= 7.7 Hz), 124.0, 85.1, 24.2. 31P{1H} NMR (CDCl3): δ 10.8 (s).
isolated using method B. Yellow solid, Method B. Yield: 98 mg
(72%); mp: 113-114.5°C; Anal. Calcd. for C 26H29BNO2PS:
Synthesis of N-ethyl-1,1-diphenyl-N-(4,4,5,5-tetramethyl-1,3,2- (461.37): C, 67.69; H, 6.34; N, 3.04. Found: C, 67.47; H, 6.14; N,
dioxaborolan-2-yl)phosphinecarboxamide (6a): This mixture 3.07. 1H NMR (CDCl3): δ 7.33-7.24 (ov m, 15H, Ar), 5.38 (s, 2H,
was allowed to stir for 18 h and the product was isolated using CH2), 0.98 (s, 12H, pin). 11B{1H} NMR (CDCl3): δ 24.5 (s). 13C{1H}
method B. White solid. Yield: 93 mg (76%); mp: 79.4-80.4°C; NMR (CDCl3): δ 224.8 (d, JCP = 46 Hz), 138.2, 138.1 (d, JCP = 3.8
Anal. Calcd. For C21H27BNO3P: (383.23): C, 65.82; H, 7.10; N, Hz), 134.9, 134.7, 129.2, 128.5, 128.4 (d, JCP = 7.7 Hz), 128.1,
1
3.65. Found: C, 65.40; H, 7.42; N, 3.58. H NMR (CDCl3): δ 7.36 127.0, 85.2, 53.8, 24.2. 31P{1H} NMR (CDCl3): δ 31.1 (s).
(m, 4H, Ar), 7.34-7.31 (ov m, 6H, Ar), 3.53 (q, J = 6.9 Hz, 2H, CH2),
1.11 (t, J = 6.9 Hz, 3H, CH3), 1.00 (s, 12H, pin). 11B{1H} NMR Synthesis of N-cyclohexyl-1,1-diphenyl-N-(4,4,5,5-tetramethyl-
(CDCl3): δ 24.5 (s). 13C{1H} NMR (CDCl3): δ 183.4 (d, JCP = 30.7 1,3,2-dioxaborolan-2-yl)phosphinecarbothioamide (11a): This
Hz), 135.9 (d, JCP = 6.7 Hz), 134.5 (d, JCP = 20.1 Hz), 129.0, 128.4 mixture was allowed to stir for 18 and the product was isolated
(d, JCP = 7.7 Hz), 84.3, 38.9, 15.4. 31P{1H} NMR (CDCl3): δ 10.9 (s). using method B. Yellow solid. Yield: 98 mg (72%); mp: 137-
138°C; Anal. Calcd. For C25H33BNO2PS: (453.39): C, 66.23; H,
1
Synthesis of N-cyclohexyl-1,1-diphenyl-N-(4,4,5,5-tetramethyl- 7.34; N, 3.09. Found: C, 65.94; H, 7.37; N, 3.16. H NMR (CDCl3):
1,3,2-dioxaborolan-2-yl)phosphinecarboxamide (7a): This δ 7.46 (m, 4H, Ar), 7.36-7.32 (ov m, 6H, Ar), 4.66 (br s, 1H, CH),
mixture was allowed to stir for 18 h where the product was 1.84 (d, J = 11.1 Hz, 2H, Cy), 1.70 (d, J = 13.1 Hz, 2H, Cy), 1.43
isolated using method A. White solid. Yield: 110 mg (78%); mp: (m, 2H, Cy), 1.32 (s, 12H, pin), 1.19 (m, 2H, Cy), 1.06 (m, 1H, Cy).
128.5-131.5°C; Anal. Calcd. For C25H33BNO3P: (437.33): C, 11B{1H} NMR (CDCl3): δ 24.4 (s). 13C{1H} NMR (CDCl3): δ 216.2 (d,
68.66; H, 7.61; N, 3.20. Found: C, 68.49; H, 7.97; N, 3.31. 1H JCP = 32.2 Hz), 135.2, 134.5 (d, JCP = 20.1 Hz), 129.5, 128.4 (d, JCP
NMR (CDCl3): δ 7.39 (m, 4H, Ar), 7.33-7.30 (ov m, 6H, Ar), 4.24 = 8.1 Hz), 85.2, 60.8 (d, JCP = 12.1 Hz), 31.4, 25.8, 25.5, 25.1.
(tt, J = 3.0 Hz, J = 0.9 Hz, 2H, CH), 1.89 (m, 2H, Cy), 1.72 (m, 2H, 31P{1H} NMR (CDCl3): δ 19.3 (br s).
Cy), 1.62-1.54 (ov m, 3H, Cy), 1.26 (m, 2H, Cy), 1.11 (m, 1H, Cy),
1.02 (s, 12H, pin). 11B{1H} NMR (CDCl3): δ 24.7 (s). 13C{1H} NMR Synthesis of N-tert-butyl-1,1-diphenyl-N-(4,4,5,5-tetramethyl-
(CDCl3): δ 183.4 (d, JCP = 29.6 Hz), 136.2 (d, JCP = 8.1 Hz), 134.5 1,3,2-dioxaborolan-2-yl)phosphinecarbothioamide (12a): This
(d, JCP = 20.1 Hz), 128.9, 128.3 (d, JCP = 8.1 Hz), 84.0, 54.3, 31.4, mixture was allowed to stir for 18 and the product was isolated
26.5, 25.5, 24.3. 31P{1H} NMR (CDCl3): δ 11.8 (s).
using method B. Yellow solid. Yield: 98 mg (72%); mp: 118-
119°C; Anal. Calcd. For C23H31BNO2PS: (427.35): C, 64.64; H,
1
Synthesis of N-tert-butyl-1,1-diphenyl-N-(4,4,5,5-tetramethyl- 7.31; N, 3.28. Found: C, 64.32; H, 7.27; N, 2.77. H NMR (CDCl3):
1,3,2-dioxaborolan-2-yl)phosphinecarboxamide (8a): This δ 7.48 (m, 4H, Ar), 7.38-7.31 (ov m, 6H, Ar), 1.67 (s, 9H, t-Bu),
mixture was allowed to stir for 2 days and the product was 1.09 (s, 12H, pin). 11B{1H} NMR (CDCl3): δ 23.4 (s). 13C{1H} NMR
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Dalton Trans, 2017, 46, 1-9 | 5
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(CDCl3): δ 135.1 (d, JCP = 4.0 Hz), 134.0 (d, JCP = 18.8 Hz), 129.3, = 13.4 Hz), 134.2 (d, JCP = 19.2 Hz), 134.2, 129.7, 128.9 (d, JCP
=
View Article Online
DOI: 10.1039/C7DT02305G
1
128.3 (d, JCP = 8.1 Hz), 85.3, 61.4 (d, JCP = 9.4 Hz), 28.2, 25.8. 6.7 Hz), 52.9, 28.8. 31P{ H} NMR (CDCl3): δ -1.6 (s).
31P{1H} NMR (CDCl3): δ 22.3 (s).
Synthesis of N-benzyl-1,1-diphenylphosphinecarbothioamide
Synthesis
of
4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl (10b): Method A. Yellow solid. Yield: 86 mg (84%); mp: 80.9-
diphenylphosphinecarboxylate (13): A benzene solution of 82.1°C; Anal. Calcd. For C20H18NPS: (319.34): C, 71.62; H, 5.41;
1
Ph2PBpin (100 mg, 0.32 mmol) was subjected to 3 freeze-pump N, 4.18. Found: C, 71.55; H, 5.51; N, 4.26. H NMR (CDCl3): δ
thaw cycles and charged with 1 atmosphere of carbon dioxide. 7.50-7.44 (m, 5H), 7.41-7.36 (ov m, 6H, Ar), 7.32-7.26 (m, 3H),
The solution was allowed to stir for 4 days. The solvent was 7.14 (dd, J = 7.8 Hz, J = 2.3 Hz, 2H, Ar), 4.89 (d, JHP = 5.0 Hz, 2H,
removed under vacuum, leaving a yellow oil, which was CH2). 13C{1H} NMR (CDCl3): δ 208.1 (d, JCP = 39.0 Hz), 135.9, 134.4
recrystallized from pentane, leaving a light yellow solid. Yield: (d, JCP = 21.5 Hz), 134.1, 130.2, 129.2 (d, JCP = 6.7 Hz), 129.0,
40 mg (35%); mp: 58-59°C; Anal. Calcd. For C 19H22BO4P: 128.1, 127.7, 50.2. 31P{1H} NMR (CDCl3): δ 16.2 (s).
1
(427.35): C, 64.07; H, 6.23. Found: C, 64.27; H, 6.27. H NMR
(C6D6): δ 7.57 (m, 4H, Ar), 7.00 (m, 6H, Ar), 0.94 (s, 12H, pin). Synthesis
of
N-cyclohexyl-1,1-diphenylphosphine-
11B{1H} NMR (C6D6): δ 22.7 (s). 13C{1H} NMR (C6D6): δ 177.5 (d, carbothioamide (11b): Method A. Yellow solid. Yield: 91 mg
JCP = 16 Hz), 135.0 (d, JCP = 20 Hz), 132.8 (d, JCP = 5 Hz), 129.8, (87%); mp: 94.0-95.4 °C; Anal. Calcd. For C19H22NPS: (327.43):
1
128.9 (d, JCP = 8 Hz), 84.2, 24.5. 31P{1H} NMR (C6D6): δ -0.7 (s).
C, 69.70; H, 6.77; N, 4.28. Found: C, 69.17; H, 7.02; N, 3.91. H
NMR (CDCl3): δ 7.48-7.38 (ov m, 10H, Ar), 4.51 (m, 1H, CH), 1.91
(m, 2H, Cy), 1.54-1.34 (ov m, 5H, Cy), 1.19-1.05 (ov m, 3H, Cy).
Preparation of compounds 1b-12b.
General Procedure: Phosphinoboration reactions were carried 13C{1H} NMR (CDCl3): δ 205.7 (d, JCP = 39.0 Hz), 134.5 (d, JCP
=
out as described above. Following the prescribed time, 14.8 Hz), 134.3 (d, JCP = 20.1 Hz), 130.1, 129.2 (d, JCP = 6.7 Hz),
methanol (5 drops) was added and the solution was stirred for 53.6, 31.2, 25.3, 24.0. 31P{1H} NMR (CDCl3): δ 14.5 (s).
an additional 30 minutes. The solvent was removed under
vacuum and the residue was either washed with hexane Synthesis
of
N-tert-butyl-1,1-diphenylphosphine-
(Method A) or recrystallized from hexane (Method B) or diethyl carbothioamide (12b): Method A. Yellow solid. Yield: 87 mg
ether (Method C).
Synthesis of
(90%); mp: 121.9-122.5°C; Anal. Calcd. For C17H20NPS: (301.39):
C, 67.75; H, 6.69; N, 4.65. Found: C, 67.99; H, 6.66; N, 4.76. H
N-(4-nitrophenyl)-1,1-diphenylphosphine- NMR (CDCl3): δ 7.46-7.39 (ov m, 10H, Ar), 7.07 (br s, 1H, NH),
1
carboxamide (5b): Washed with cold diethyl ether (3x5 mL). 1.43 (s, 9H, t-Bu). 13C{1H} NMR (CDCl3): δ 206.3 (d, JCP = 40.3 Hz),
Yellow solid. Yield: 88 mg (78%); mp: 149.5-151 °C (decomp.). 135.2 (d, JCP = 17.5 Hz), 134.2 (d, JCP = 20.2 Hz), 130.1, 129.2 (d,
Anal. Calcd. For C19H15N2O3P: (350.31): C, 65.14; H, 4.32; N, 8.00. JCP = 8.1 Hz), 57.6, 27.7. 31P{1H} NMR (CDCl3): δ 17.4 (s).
1
Found: C, 65.01; H,4.44 ; N, 8.18. H NMR (CDCl3): δ 8.14 (dm, J
= 9.2 Hz, 2H, Ar), 7.61-7.56 (ov m, 5H, Ar, NH), 7.53 (dm, J = 9.2 X-ray diffractions studies
Hz, 2H, Ar), 7.49-7.43 (ov m, 6H, Ar). 13C{1H} NMR (CDCl3): δ Crystals for investigation were covered in Nujol®, mounted into
177.6 (d, JCP = 20.1 Hz), 143.8, 143.0, 134.6 (d, JCP = 20.1 Hz), a goniometer head, and then rapidly cooled under a stream of
132.2 (d, JCP = 9.6 Hz), 130.6, 129.4 (d, JCP = 7.7 Hz), 125.2, 125.2, cold N2 of the low-temperature apparatus (Oxford Cryostream)
119.0. 31P{1H} NMR (CDCl3): δ 1.9 (s).
attached to the diffractometer. The data were then collected
using the APEXIII software suite27 on a Bruker Photon 100 CMOS
Synthesis of N-ethyl-1,1-diphenylphosphinecarboxamide ( 6b): diffractometer using a graphite monochromator with Mo-Kα
Method A. White solid. Yield: 78 mg (94%); mp: 81.3-82.8 °C; radiation (λ = 0.71073 Å). For each sample, data were collected
Anal. Calcd. For C15H16NOP: (257.27): C, 70.01; H, 6.30; N, 5.43. at low temperature. APEX-III software was used for data
1
Found: C, 69.79; H, 6.39; N, 5.57. H NMR (CDCl3): δ 7.54-7.48 collection and reduction and SADABS28 was used for absorption
(m, 4H, Ar), 7.40-7.37 (ov m, 6H, Ar), 5.66 (br s, NH), 3.32 (qd, J corrections (multi-scan; semi-empirical from equivalents).
= 6.9 Hz, JHP = 5.5 Hz, 2H, CH2), 1.05 (t, J = 6.9 Hz, 3H, CH3). XPREP was used to determine the space group and the
13C{1H} NMR (CDCl3): δ 177.0 (d, JCP = 12.7 Hz), 134.4 (d, JCP
=
structures were solved and refined using the SHELX 29 software
18.5 Hz), 133.7 (d, JCP = 11.6 Hz), 129.8, 129.0 (d, JCP = 8.1 Hz), suite as implemented in the WinGX30 program suites. Validation
35.0, 15.0. 31P{1H} NMR (CDCl3): δ -3.4 (s).
of the structures was conducted using PLATON. 32 All carbon-
bound hydrogen atoms were modelled in idealized geometries
Synthesis of N-tert-butyl-1,1-diphenylphosphinecarboxamide using riding models in which temperature factor was
(8b): Method A. White solid. Spectroscopic data matches that determined by the carbon atom to which it was bonded. For
which has been previously reported,5 however since full the structures containing N-H bonds, the nitrogen-bound H
spectroscopic details have not been reported for this atoms were modelled freely using isotropic temperature
compound, they are presented here. Yield: 83 mg (91%); mp: factors. Crystallographic information has also been deposited
119.2-120.8 °C; Anal. Calcd. For C17H20NOP: (285.33): C, 71.56; with the Cambridge Crystallographic Data Centre (CCDC
H, 7.07; N, 4.91. Found: C, 71.77; H, 7.17; N, 5.01. 1H NMR 1549899-1549904). Copies of the data can be obtained free of
(CDCl3): δ 7.52-7.47 (m, 4H, Ar), 7.40-7.35 (ov m, 6H, Ar), 5.51 charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from
(br s, NH), 1.28 (s, 9H, t-Bu). 13C{1H} NMR (CDCl3): δ 176.1 (d, JCP the Cambridge Crystallographic Data Centre, 12 Union Road,
6 | Dalton Trans., 2017, 46, 1-9
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2016, 80, 2148–2154. (d) D. J. Faizi, A. J. Davis, F. B. Meany
and S. A. Blum, Angew. Chem. Int. EDdO.I,: 1200.11063V,9ie/5Cw57AD,rtTi1c0l4e22O380nl56inG–e
14290. (e) M. G. Civit, J. Royes, C. M. Vogels, S. A. Westcott, A.
B. Cuenca and E. Fernández, Org. Lett., 2016, 18, 3830–3833.
(a) X. Sanz, C. M. Vogels, A. Decken, C. Bo. S. A. Westcott and
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G. Civit, X. Sanz, C. M. Vogels, C. Bo, S. A. Westcott and E.
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(a) T. Itoh, T. Matsuedo, Y. Shimizu and M. Kanai, Chem. Eur.
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Cambridge CB2 1EZ, UK; fax: + 44 1223 336033 or e-mail:
deposit@ccdc.cam.ac.uk).
6
7
Conflict of Interests
There are no conflicts of interest to declare.
Acknowledgements
8
9
CLBM, DWS and SAW thank the Natural Sciences and
Engineering Research Council of Canada for funding as well as
the University of Windsor, the University of Toronto and Mount
Allison University. DWS and SAW are grateful for the award of
Canada Research Chairs. DWS is also grateful for the award of
an Einstein Fellowship at TU Berlin. DZ thanks Mount Allison
University for a summer research award. We are also grateful
to the technical assistance of Dan Cutthumb Durant (MAU) and
anonymous reviewers are thanked for their very helpful
comments.
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PAPER
Table 1 Crystallographic data collection parameters for 1a, 2a, 6a, 8a, 7b and 12a
Complex
1a
C33H36BN2O2P
534.42
2a
6a
C21H27BNO3P
383.21
8a
7b
C19H22NOP
311.34
12a
C23H31BNO2PS
427.33
Formula
C25H36BN2O2P
438.34
C23H31BNO3P
411.27
Molecular weight
Crystal system
Triclinic
Triclinic
Triclinic
P-1
Triclinic
P-1
Orthorhombic
Iba2
Triclinic
Space group
P-1
P-1
P-1
a/Å
b/Å
c/Å
α/o
β/o
γ/o
9.6725(4)
11.3305(4)
14.4827(6)
101.512(2)
100.403(2)
101.893(2)
1480.66(10)
2
10.7605(4)
11.2811(4)
12.5055(4)
111.6550(10)
98.380(2)
110.8890(10)
1249.14(8)
2
6.2343(10)
9.4532(13)
17.992(3)
86.725(5)
89.957(6)
84.737(5)
1054.1(3)
2
9.5854(7)
9.7989(8)
15.9177(14)
75.187(3)
80.891(3)
63.041(3)
1286.77(18)
2
10.6648(7)
34.271(2)
9.4843(6)
90
10.3603(12)
17.1280(19)
26.966(3)
92.761(4)
93.308(4)
90.282(4)
4771.5(9)
8
90
90
V/Å3
Z
3466.4(4)
8
ρ
calc./Mg m-3
1.199
1.165
1.207
1.061
1.193
1.190
Crystal size/mm3
0.237 x 0.193 x 0.06
0.474 x 0.126 x
0.055
0.607 x 0.194 x
0.087
0.611 x 0.189 x
0.063
0.4 x 0.3 x 0.2
0.724 x 0.341 x
0.070
Temp/K
Radiation/Å
µ/mm-1
173(2)
Mo-Kα (λ=0.71073)
0.125
173(2)
170(2)
170(2)
143(2)
Mo-Kα (λ=0.71073)
0.160
170(2)
Mo-Kα (λ=0.71073)
Mo-Kα (λ=0.71073)
Mo-Kα (λ=0.71073)
Mo-Kα (λ=0.71073)
0.221
0.133
29421
5350
0.150
45511
6150
0.127
65255
7499
Total reflections
25932
12728
213108
Total unique
reflections
5701
3235
26943
No. of variables
538
288
249
282
203
1128
θ Range/o
2.902 to 25.847
0.220 and -0.291
3.114 to 26.862
0.264 and -0.282
3.046 to 29.999
0.297 and -0.259
3.174 to 29.999
0.557 and -0.391
3.110 to 27.494
0.788 and -0.427
2.780 to 29.709
1.241 and -0.524
Largest difference
peak/hole/e Å-3
S (GoF) on F2
1.032
0.0430
0.0961
1.048
0.0447
0.1012
1.041
0.0374
0.0952
1.041
0.0417
0.1158
1.202
0.0487
0.1301
1.103
0.0593
0.1517
R1
wR2b (all data)
a) R1 = ∑||Fo|–|Fc||/∑|Fo|. b) wR2 = (∑[w(Fo2−Fc2)2]/∑[wFo4])1/2, where w = 1/[σ2(Fo2) + (0.0339P)2 + (0.6260P)] (1a), 1/[σ2(Fo2) + (0.0421P)2 + (0.3982P)] (2a), 1/[σ2(Fo2) +
(0.0384P)2 + (0.4300P)] (6a), 1/[σ2(Fo2) + (0.1154P)2 + (1.0730P)] (8a), 1/[σ2(Fo2) + (0.0525P)2 + (4.3794P)] (7b), and 1/[σ2(Fo2) + (0.0494P)2 + (5.9060P)] (12a), where P =
(max (Fo2, 0) + 2·Fc2)/3.
This journal is © The Royal Society of Chemistry 20xx
Dalton Trans, 2017, 46, 1-9 | 10
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Page 11 of 11
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT02305G
The transition metal-free addition of phosphinoboronate ester Ph2PBpin (pin = 1,2-
O2C2Me4) to heterocumulenes including carbodiimides, isocyanates, isothiocyanates
and carbon dioxide proceeds with remarkable selectivity to give products in high yield.
O
O
E
Bpin
EH
E
C
E
MeOH
P
B
Ph
Ph
E
C
E
C
PPh2
PPh2
no added catalyst
or base required
Ph2PBpin